Insights into the Structure of Cyclohexane from Femtosecond Degenerate Four-Wave Mixing Spectroscopy and Ab Initio Calculations

Christoph Riehn, Victor V. Matylitsky, Wlłodzimierz Jarzȩba, Bernd Brutschy, Tarakeshwar Pilarisetty, Kwang S. Kim

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

In this paper, we report the use of femtosecond time-resolved degenerate four-wave mixing rotationally resolved spectroscopy to obtain very accurate structural information on the symmetric top cyclohexane. Apart from highlighting the versatility of this method in determining accurate structures of large and complex molecules without dipole moment, the present study also details the comparison of the experimentally determined rotational constant B0 with that obtained from high-level ab initio calculations. The theoretical calculations, which were carried out at both the second-order Moøller-Plesset (MP2) and coupled-cluster with single, double, and perturbative triple substitutions [CCSD(T)] levels of theory, also take into account vibrational averaging effects. A detailed investigation of the vibrational averaging effects reveals that the corrections emerge from only the six highly symmetric A1g modes, a justification of which is provided by an analysis of these modes.

Original languageEnglish (US)
Pages (from-to)16455-16462
Number of pages8
JournalJournal of the American Chemical Society
Volume125
Issue number52
DOIs
StatePublished - Dec 31 2003
Externally publishedYes

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Four wave mixing
Cyclohexane
Spectrum Analysis
Spectroscopy
Dipole moment
Substitution reactions
Molecules

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Insights into the Structure of Cyclohexane from Femtosecond Degenerate Four-Wave Mixing Spectroscopy and Ab Initio Calculations. / Riehn, Christoph; Matylitsky, Victor V.; Jarzȩba, Wlłodzimierz; Brutschy, Bernd; Pilarisetty, Tarakeshwar; Kim, Kwang S.

In: Journal of the American Chemical Society, Vol. 125, No. 52, 31.12.2003, p. 16455-16462.

Research output: Contribution to journalArticle

Riehn, Christoph ; Matylitsky, Victor V. ; Jarzȩba, Wlłodzimierz ; Brutschy, Bernd ; Pilarisetty, Tarakeshwar ; Kim, Kwang S. / Insights into the Structure of Cyclohexane from Femtosecond Degenerate Four-Wave Mixing Spectroscopy and Ab Initio Calculations. In: Journal of the American Chemical Society. 2003 ; Vol. 125, No. 52. pp. 16455-16462.
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